CN112429701A - 一种用于水解制氢的废硅片处理方法 - Google Patents
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 96
- 239000010703 silicon Substances 0.000 title claims abstract description 96
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 77
- 239000002184 metal Substances 0.000 claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- -1 cleaning Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010030 laminating Methods 0.000 claims abstract description 8
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims abstract description 8
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 claims abstract description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001119 stannous chloride Substances 0.000 claims abstract description 4
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 4
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229960002799 stannous fluoride Drugs 0.000 claims abstract description 4
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims abstract description 3
- 239000006255 coating slurry Substances 0.000 claims abstract description 3
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims abstract description 3
- 235000012431 wafers Nutrition 0.000 claims description 65
- 238000003825 pressing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical class [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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Abstract
本发明公开了一种用于水解制氢的废硅片处理方法;以废硅片为原料,经清洗、浆料涂抹、烘干、与金属片叠片、压片、热处理,获得硅基制氢材料;浆料为还原金属粉、低熔点金属盐、粘结剂和有机溶剂的混合物;还原金属粉为镁、铝、锌的一种或几种;低熔点金属盐为锡卤盐、铋卤盐的一种或几种;锡卤盐为氯化亚锡、氯化锡、溴化锡、溴化亚锡、氟化亚锡的一种或几种;铋卤盐为氯化铋、溴化铋、碘化铋的一种或几种;有机溶剂为丙酮、丁酮、戊酮、己酮、环戊酮、环己酮的一种或几种;金属片为锂、镁、铝和锌片的两种或几种,且必含有锂片;该硅基制氢材料具有很好的水解性能,在制氢领域具有很好的应用前景。
Description
技术领域
本发明专利属于制氢领域,具体涉及一种用于水解制氢的废硅片处理方法。
背景技术
近20年来,随着太阳能电池的迅猛发展,以硅片为主导的太阳能电池迎来报废期,越来越多的废旧硅片堆积如山,给环境带来了污染。废旧硅片的回收和再利用已经成为各国政府和科研人员亟待解决的关键问题。废旧硅片回收利用的常见方法有:1)硅片剔除表面的瑕疵,可重新用于太阳能电池的硅片来源;2)硅片氧化处理成二氧化硅,作为硅的原材料,重新再生产;3)硅片作为其它用途,比如作为制氢材料,可提供可观的氢气。文献报道,废旧硅片与强碱溶液反应,可以提供1-3wt%的便携式氢源,而产物二氧化硅又可以用作硅的原材料。但是,强碱的腐蚀性对设备材质要求较高,也对使用者带来一定危害。而硅的化学活性低以及不溶性产物二氧化硅的阻碍作用,导致硅无法在中性水溶液中持续反应。
发明内容
针对现有技术方案的缺陷,本发明的目的是提供一种用于水解制氢的废硅片处理方法,克服现有制备技术的缺陷,提高硅材料的化学活性。
1.为实现上述发明目的,本发明的技术方案是:一种用于水解制氢的废硅片处理方法,其特征在于:以废硅片为原料,经清洗、浆料涂抹、烘干、与金属片叠片、压片、热处理,获得硅基制氢材料;浆料为还原金属粉、低熔点金属盐、粘结剂和有机溶剂的混合物;还原金属粉为镁、铝、锌的一种或几种;低熔点金属盐为锡卤盐、铋卤盐的一种或几种;锡卤盐为氯化亚锡、氯化锡、溴化锡、溴化亚锡、氟化亚锡的一种或几种;铋卤盐为氯化铋、溴化铋、碘化铋的一种或几种;有机溶剂为丙酮、丁酮、戊酮、己酮、环戊酮、环己酮的一种或几种;金属片为锂、镁、铝和锌片的两种或几种,且必含有锂片;金属片是锂片与其它金属片压制而成,且锂片是其它金属片质量的5-50wt%;
一种用于水解制氢的废硅片处理方法,包括:
1)裁剪废硅片,用去离子水清洗干净,烘干;
2)称量一定质量的还原金属粉、低熔点金属盐、粘结剂和有机溶剂,搅拌混合,配置浆料;并将浆料按一定比例涂抹在步骤1)废硅片的正反两面;还原金属粉为硅片质量的30-150wt%,低熔点金属盐为硅片质量的1-30wt%;粘结剂为硅片质量的1-15wt%;
3)将金属片与步骤2)硅片叠片,每张硅片夹在两张金属片之间,且金属片全覆盖硅片,金属片与硅片面积的比值1.01-1.5;硅片的数量为1-5片,金属片的数量为3-6片;金属片为硅片质量的50-200wt%;
4)将步骤3)的产物压制成块;
5)4)将步骤4)的产物在惰性气体中热处理1-20h;热处理温度为300-8000C;然后自然冷却到常温;获得硅基制氢材料。
本专利设计一种用于水解制氢的废硅片处理方法;通过硅合金化和盐掺杂,提高硅的化学反应活性;以还原金属粉、低熔点金属盐、粘结剂和有机溶剂制备浆料;再把浆料涂抹在硅片;再将金属片与硅片叠片,压制成块;产物在高温中会发生还原金属与盐的置换反应,金属与硅的合金化反应;与现有技术相比,本发明专利提供的一种用于水解制氢的废硅片处理方法,具有以下优势:
1)制备工艺简单、工序可控、可产业化生产;
2)废硅片再利用,有利于减少环境污染;硅基制氢材料化学活性高,水解条件温和,产氢量大;
3)还原金属粉、低熔点金属盐与粘结剂制成浆料涂抹在硅片表面以及金属片与硅片压制成块,有利于硅、其它金属和盐充分接触;有利于降低硅合金化反应温度;
4)采用锂等其它还原金属和铋、锡低熔点盐的置换反应,产生低熔点铋、锡与锂、其它还原金属形成低熔点合金,再与硅结合,有利于形成金属盐分散在硅合金表面的结构;该结构在水解过程中易形成高浓度金属盐溶液的微腐蚀区域,极大提高了硅合金的化学反应活性;该硅基制氢材料在制氢领域具有很好的应用前景。
具体实施方式
为能进一步了解本发明的发明内容、特点及功效,兹举以下实施例详细说明如下:
实例1
一种用于水解制氢的废硅片处理方法,包括:
1)裁剪废硅片,用去离子水清洗干净,烘干;
2)称量一定质量的还原金属粉、低熔点金属盐、粘结剂和有机溶剂,搅拌混合,配置浆料;并将浆料按一定比例涂抹在步骤1)废硅片的正反两面;
3)将金属片与步骤2)硅片叠片,每张硅片夹在两张金属片之间,且金属片全覆盖硅片,金属片与硅片面积的比值1.1;硅片的数量为1片,金属片的数量为2片;
4)将步骤3)的产物压制成块;
5)4)将步骤4)的产物在惰性气体中热处理5h;热处理温度为6000C;然后自然冷却到常温;获得硅基制氢材料。
废硅片的成分设计,包括:
1)1块硅片,48.2g;铝粉,30g;氯化亚锡,5g;粘结剂,2g;2块金属片,100g(其中锂片,10g;铝片90g);有机溶剂为丙酮;
2)1块硅片,47.4g;镁粉,20g;氟化亚锡,4g;粘结剂,1.5g;2块金属片,100g(其中锂片,8g;镁带92g);有机溶剂为丙酮;
水解实验显示,该硅基制氢材料在50°热水中具有很好的水解性能。
实例2
一种用于水解制氢的废硅片处理方法,包括:
6)裁剪废硅片,用去离子水清洗干净,烘干;
7)称量一定质量的还原金属粉、低熔点金属盐、粘结剂和有机溶剂,搅拌混合,配置浆料;并将浆料按一定比例涂抹在步骤1)废硅片的正反两面;
8)将金属片与步骤2)硅片叠片,每张硅片夹在两张金属片之间,且金属片全覆盖硅片,金属片与硅片面积的比值1.05;硅片的数量为2片,金属片的数量为3片;
9)将步骤3)的产物压制成块;
10)4)将步骤4)的产物在惰性气体中热处理10h;热处理温度为5000C;然后自然冷却到常温;获得硅基制氢材料。
废硅片的成分设计,包括:
3)2块硅片,97.6g;铝粉,40g;溴化锡,5g,氯化铋,10g;粘结剂,5g;3块金属片,150g(其中锂,15g;铝片135g);有机溶剂为丙酮;
4)2块硅片,98.2g;镁粉,20g;氯化锡,4g,溴化铋,8g;粘结剂,1.5g;2块金属片,150g(其中锂,20g;镁带130g);有机溶剂为己酮
水解实验显示,该硅基制氢材料在50°热水中具有很好的水解性能。
实例3
实施步骤如实例1
废硅片的成分设计,包括:
5)2块硅片,97.4g;锌粉,40g;溴化锡,3g,氯化铋,6g;粘结剂,4g;3块金属片,150g(其中锂,20g;铝片135g);有机溶剂为丁酮;
6)2块硅片,98.0g;镁粉,20g;氯化铋,4g,溴化铋,8g;粘结剂,3g;3块金属片,150g(其中锂,8g;镁带92g);有机溶剂为戊酮
7)2块硅片,97.98g;镁粉,20g;氯化铋,4g,溴化亚锡,8g;粘结剂,3g;3块金属片,148g(其中锂,20g;锌片128g);有机溶剂为丙酮
水解实验显示,该硅基制氢材料在50°热水中具有很好的水解性能。
上述专利的具体实施方式是示例性的,是为了更好的使本领域技术人员能够理解本专利,不能理解为是对本专利包括范围的限制;只要是根据本专利所揭示精神的所作的任何等同变更或修饰,均落入本专利包括的范围。
Claims (1)
1.一种用于水解制氢的废硅片处理方法,其特征在于:以废硅片为原料,经清洗、浆料涂抹、烘干、与金属片叠片、压片、热处理,获得硅基制氢材料;浆料为还原金属粉、低熔点金属盐、粘结剂和有机溶剂的混合物;还原金属粉为镁、铝、锌的一种或几种;低熔点金属盐为锡卤盐、铋卤盐的一种或几种;锡卤盐为氯化亚锡、氯化锡、溴化锡、溴化亚锡、氟化亚锡的一种或几种;铋卤盐为氯化铋、溴化铋、碘化铋的一种或几种;有机溶剂为丙酮、丁酮、戊酮、己酮、环戊酮、环己酮的一种或几种;金属片为锂、镁、铝和锌片的两种或几种,且必含有锂片;金属片是锂片与其它金属片压制而成,且锂片是其它金属片质量的5-50wt%;一种用于水解制氢的废硅片处理方法,包括:
1)裁剪废硅片,用去离子水清洗干净,烘干;
2)称量一定质量的还原金属粉、低熔点金属盐、粘结剂和有机溶剂,搅拌混合,配置浆料;并将浆料按一定比例涂抹在步骤1)废硅片的正反两面;还原金属粉为硅片质量的30-150wt%,低熔点金属盐为硅片质量的1-30wt%;粘结剂为硅片质量的1-15wt%;
3)将金属片与步骤2)硅片叠片,每张硅片夹在两张金属片之间,且金属片全覆盖硅片,金属片与硅片面积的比值1.01-1.5;硅片的数量为1-5片,金属片的数量为3-6片;金属片为硅片质量的50-200wt%;
4)将步骤3)的产物压制成块;
5)4)将步骤4)的产物在惰性气体中热处理1-20h;热处理温度为300-800℃;然后自然冷却到常温;获得硅基制氢材料。
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CN107188124A (zh) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | 一种硅基制氢材料的制备方法 |
CN107195895A (zh) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | 一种以合金为还原剂的硅基材料制备方法 |
CN107188123A (zh) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | 一种硅/碱金属制氢材料的制备方法 |
CN110592433A (zh) * | 2019-08-06 | 2019-12-20 | 上海交通大学 | 一种半固态金属基水解制氢材料及制备方法 |
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JP2006240935A (ja) * | 2005-03-04 | 2006-09-14 | Sharp Corp | 水素ガスの製造方法 |
US20100150826A1 (en) * | 2005-08-09 | 2010-06-17 | The University Of British Columbia | Microporous metals and methods for hydrogen generation from water split reaction |
CN107188124A (zh) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | 一种硅基制氢材料的制备方法 |
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